Electrochemistry

(Electrode Potential)
Dr.S.SURESH
Assistant Professor
Email:avitsureshindia@gm
ail.com

Electrode potential
The tendency of a metal to get oxidised or
reduced when it is placed in a solution of its own
salt is called electrode potential.
When a metal [M] is placed in a solution
containing its own ions [Mn+], then the metal may
undergo either oxidation or reduction. If the
metal undergoes oxidation, then the positive
metal ions may pass into the solution
M
Mn+ + ne
If the metal undergoes reduction, then the
negative ions may get deposited over the metal.
Mn+ + ne

Zn in
ZnSO4
When Zn is placed in a solution of
its own salt, zinc undergoes
oxidation with the release of
electrons. The electrons liberated
in the process, accumulate over the
surface of the metal and hence, the
metal is negatively charged. Now,
the negatively charged metal
attracts the positive ions from the
solution, and hence formation of a
double layer takes place near the
surface of the metal.

Cu in
CuSO4
When Cu is placed in the
solution
of
CuSO4,
the
copper ions in the solution
gets deposited over the
metal and hence the metal
becomes positively charged.
The
positively
charged
metal
attracts
the
negatively charged sulphate
ions in the solution and
hence a doubly charged
layer (Helmholtz electrical
double layer) is formed near
the metal.

Single Electrode Potential:

It is a measure of tendency of a metallic
electrode to lose or gain electrons when it
is in contact with a solution of its own salt.

Standard Electrode Potential:

It is a measure of tendency of a metallic
electrode to lose or gain electrons, when it is
in contact with a solution of its own salt of 1
Molar concentration at 25C.

Primary Reference
Electrodes
The electrode potential is found out by
coupling the electrode with a primary
reference electrode, the potential of
which is arbitrarily fixed as zero. The
important primary reference electrode
used is a standard hydrogen electrode,

Standard hydrogen
electrode(SHE)
It consists of a platinum
wire in a inverted glass
tube. Hydrogen gas is
passed through the tube
at 1 atm. A platinum foil is
attached at the end of the
wire. The electrode is
immersed in 1M H+ ion
solution at 25C. The
electrode potential of SHE
is
zero
at
all
temperatures.

Standard hydrogen
electrode(SHE)
It is represented as
Pt, H2 (1atm)/H+ (1M)
In a cell when the standard hydrogen electrode
acts as anode, the electrode reaction can be
written as
H2(g)
2 H + + 2 e
When the standard hydrogen electrode acts as
cathode, the electrode reaction can be written as
2H+
+ 2e
H2(g)
Based on the electrode potential obtained with
reference to hydrogen, electrochemical series is
obtained.

Secondary Reference Electrode:

(Saturated calomel electrode)

Need for Secondary Reference

Electrode
The use of SHE is difficult, because it is difficult
to maintain 1M H+ ion concentration and the
pressure of the gas at one atmosphere. Also,
the electrode will easily get poisoned in case
of traces of impurities in the gas and hence,
other reference electrodes are used.
Example: Saturated calomel electrode (Saturated
KCl)

Saturated calomel
electrode
It
is
a
commonly
used
reference electrode, it consists
of a glass tube, that contains
Hg at the bottom covered with
solid Hg2Cl2 and above this the
tube is filled with KCl solution.
A platinum wire is in touch
with Hg and it is used for
electrical contact. The KCl
solution inside the tube can
have
ionic
contact
with
solution outside and acts as a
salt bridge.
The electrode potential of the
calomel electrode is +0.2422V.

Determination of standard electrode potential

of Silver using Saturated Calomel Electrode
To determine the electrode potential of Silver (electrode)
immersed in 1M solution of AgCl, the Ag half cell is
connected with the calomel half cell, through a salt bridge of
potassium chloride. Since the reduction potential of the
coupled Ag electrode is more than E of calomel electrode
(+0.2422V), the calomel electrode behaves as anode and Ag
acts as cathode

Determination of standard
electrode potential of Zinc
The cell may be represented as
Hg, Hg2Cl2(s) KCl (Sat.Sol.) // AgCl (1M), Ag
The EMF of this cell, is measured
potentiometrically. At 25C, it is found
to be 0.56 V. E R - E L
ECell =
0.56 = ER - 0.2422
EAg = 0.56 + 0.24
EAg = 0.8022 V

Electromotive
series
Definition:
When the metals (electrodes) are
arranged in the order of their
increasing
values
of
standard
reduction potential on the hydrogen
scale, then the arrangement is called
electromotive series.

Electromotive
series

Electrode
E

Electrode Reaction

Applications of Electromotive
series
The standard EMF of the cell can be calculated if the
standard electrode potential values are known.
Ecell = ER EL
The relative tendency of metals to go into the solution
can be noted with the help of electrochemical series.
Metals on the top are more easily ionised into solution.
The anode or more active metal with high negative
electrode potential in the series are more prone to
corrosion. The cathode or more noble metals with less
negative electrode potential are less prone to corrosion

Applications of Electromotive
series
Using electrochemical series we can predict
whether a metal will displace another metal from
its salt solution or not.
Example: Zinc metal having low reduction
potential in the series is easily oxidised to Zn 2+,
while copper having higher reduction potential in
the series is easily reduced to copper.
Metals hydrogen displacement behaviour can be
predicted. Any metal that like above hydrogen in
the electrochemical series can liberate hydrogen
from an acid solution.
Example: Zn lying above hydrogen in the
2
electrochemical
Zn series
H Znreacts
H 2 with dilute H 2SO4 to
liberate hydrogen.

Electrochemical cell (or)

Galvanic cell
A galvanic cell is an electrochemical cell
in which the electrons are transferred
due to redox reaction to get electrical
energy. In a galvanic cell, two different
electrodes are kept immersed in their
respective salt solutions and connected
by means of a salt bridge
Example: Daniel cell

Daniel
Cell
When a zinc rod in contact with 1M
ZnSO4 and a Cu rod in contact with 1M
CuSO4 are connected, Zn goes into the
solution as Zn2+ ions and the electrons
released flows through the external wire
reaches the copper electrode where
copper gets reduced. A salt bridge is
used
to
maintain
the
electrical
Zn between
Zn + 2e the two
E = - 0.76
V
continuity
half
cells,
also Cuit + 2e
eliminates
the liquid
junction
Cu
E = + 0.34 V
potential.
2+

2+

Zn +

Cu2+

Zn2+ + Cu

ECell = 1.10 V

REPRESENTATION OF A GALVANIC CELL

The following conventions are used in representing an

electrochemical cell:
1.

A galvanic cell is represented by writing the anode

(where oxidation occurs) on the left hand side and
cathode (where reduction occurs) on the right hand
side.
Anode // Cathode

2.

The anode of the cell is represented by writing metal

first and then the electrolyte (or the cation of the
electrolyte)
Zn/Zn2+

Representation of a Galvanic
cell
3.The cathode is represented by writing the
electrolyte first and then metal.
Cu2+/Cu
4.The two half cells are separated by a salt bridge,
which is indicated by two vertical lines.
Zn/ZnSO4 // CuSO4/Cu
or
Zn/Zn2+// Cu2+/Cu